Emulsion polish systems



3,511,797 EMULSION POLISH SYSTEMS Herbert J. Mellan and Daniel J. Kay, Buffalo, N.Y., assignors to Hooker Chemical Corporation, Niagara Falls, N.Y., a corporation of New York No Drawing. Continuation-impart of application Ser. No. 651,963, July 10, 1967. This application Feb. 17, 1969, Ser. No. 799,912

Int. Cl. 'C08f 45/52; C08g 17/16, 17/18 US. Cl. 260-285 9 Claims ABSTRACT OF THE DISCLOSURE A resinous alkali soluble polymerized partial ester product which comprises (A) a polyol polyester comprised of saturated aliphatic glycol residues connected by ester linkages to dicarboxylic residues selected from the group consisting of terephthalic acid, isophthalic acid, phthalic acid, phthalic anhydride, endo-cis-bicyclo-(2.2.1) hept--ene-2,3-dicarboxylic acid, endo-cis-bicyclo-(2.2.1) hept-5-ene-2,3-dicarboxylic anhydride, tetrahydrophthalic acid, tetrahydrophthalic anhydride, hexahydrophthalic acid, hexahydrophthalic anhydride, and mixtures thereof, with the mole ratio of said glycol compound to said dicarboxylic compound being from slightly over one-to-one to two-to-one, said residues having been subsequently connected by ester linkages to (B) tricarboxylic monoaromatic residues a portion of whose carboxyl radicals non-esterified with the said polyol polyester are esterified with a saturated fatty alcohol having 8 'to 20 carbon atoms in an amount of from about 0.05

to about 0.50 moles of fatty alcohol for each mole of tricarboxylic compound, and the remainder of the carboxyl radicals on the tricarboxylic compound are in the form selected from the group of free carboxyl and anhydride groups and said partial ester product being characterized by an acid number from about 105 to about 250, a molecular weight from about 450 to This-is a continuation-in-part of Ser. No. 284,819, filed June 3, 1963, now abandoned, and Ser. No. 615,963, filed July 10, 1967 and now abandoned.

This invention relates to resins which .are soluble in aqueous ammonia, for use in emulsion polish systems and to a process for producing such resins. In another aspect the invention relates to improved emulsion polish systems. Emulsion polishes are sometimes referred to as high resin formulas or polymer type formulas. These formulas contain as the principal ingredient, a polymer emulsion which may be a modified polystyrene, a modified polyacrylic, a blend of the two, or a complex styrene acrylic copolymer. The balance of the polish usually comprises the following components: a synthetic waxy polymer, an ammonia soluble resin, an emulsifying agent, and a diluent comprising water and a basic component such as ammonia or organic amine. Modified polystyrene emulsions are not, themselves, film formers. A deposition of an emulsion thereof on a surface normally yields a powdery residue. The use of a plasticizer reduces this tendency to some extent, but does not make the particles sufficiently cohesive to give a continuous film. To insure the proper functioning of the small particle size modified polystyrene emulsion, it has been United States Patent 0 3,511,797 Patented May 12, 1970 ice found desirable to provide a redispersible film forming matrix.

Ammonia soluble resins and synthetic waxy polymers, such as emulsifiable polyethylene, are the major components of the film forming matrix. The matrix should be water repellent, hard enough to prevent embedment, flexible to prevent surface cracking or glazing, cohesive and adhesive enough to hold the film to the floor surface. The waxy component is dispersed in the water with the aid of emulsifying agent and the basic component. The resin should be soluble in the basic emulsion system wherein it serves to improve the gloss and hardness of the polish and functions as a binder and leveling agent. A number of polymers have been used as the ammonia soluble resinsuch as low molecular weighl polyols, maleic anhydride and fumaric acid condensation products of polyhydric compounds, shellac and casein. Many of the resins used in the prior art have imparted a dark color to the finish polishand hence have resulted in a darkening of the surfaces, such at wood floors and compositiion floors such as linoleum rubber, vinyl tile and the like, on which the polist y is applied. Likewise, resins used heretofore have 1101 imparted desired water resistance to the emulsion polishes Accordingly, it is an object of this invention to pro vide an improved ammonia soluble resin for use it emulsion systems, as well as a process for producing such a resin. Another object of the invention is t( provide a resin emulsion that is very light in color Another object is to provide an emulsion polish having superior water resistance and excellent. gloss and hardness. A further object is to provide'an emulsion polisl with greatly improved storage stability. Still anothe1 object is to make an emulsion resin that servesa: a superior leveling agent in an emulsion polish. Othe1 objects and advantages will become apparent from thi: specification.

In accordance with this invention, there are providec superior alkali soluble resins having a slight or relative ly low degree of cross-linking that are suitable for use in emulsion polish systems, which comprise an alkal soluble polymerized partial ester having a low molecula: weight polyol polyester connected by ester-linkages tt tricarboxylic aromatic acid residues having thereor radicals independently selected from the group consist ing of carboxylic acid and esterified saturated fatty a1 cohol including the group 1 i:-oR wherein R is the balance of the fatty alcohol. Thest resins may be prepared by reacting selected dicarboxylit aromatic acids or anhydrides with an excess of dihy droxy saturated glycols to prepare a low molecular weigh polyol polyester. This is then reacted with tricarboxylil aromatic acid or anhydride and saturated fatty alcohols preferably simultaneously. The idealized structure of the invented resins may bl generalized as being of the type wherein A is COOH and COOR where R is saturatet fatty alkyl, T is the nucleus of the tricarboxylic com pound, E is the low molecular weight polyol polyester and n is from 1 to 10. It is to be appreciated that th A radical may also be utilized as a site for Cross-link ing and that E may optionally be a dihydroxy saturatet aliphatic compound. Further illustration of the abovt idealized structure may be had by considering one em bodiment of the invention wherein propylene glycol am isophthalic acid are esterified to form the polyol poly d-o- O (Lani I rein A may be either carboxylic acid or esterifietl ryl alcohol and n is from 1 to 10. However, the '01 polyester may also have a longer chain length contain mixed acid residues or be only the aliphatic roxylcompound. Additionally A may be utilized as te for cross-linking.

has been found that small amounts of fatty alcohols :er a very desirable but unexpected property to the nted resins. The monofunctional fatty alcohols con- ;uperior hydrophobic properties to'the invented resins ddition to serving as a means of controlling molecular ght. Fatty alcohols suitable for this invention may :haracterized as saturated, linear, primary alcohols ng from8 to 20' carbon atoms. Preferably these alls will contain from 10 to 20 carbon atoms. The nted resins contain. from about 0.05 to about 0.50 es of fatty alcohol for each mole of tricarboxylic or anhydride in the resin. Preferably the resin has 1 about 0.10 to about 0.30 mole of fatty alcohol for 1 mole of tricarboxylie acid or anhydride. For the rose of this invention glycerol monostearate, the rein product of stearic acid and glycerine, may be loyed as a means of indirectly introducing fatty us to the invented resins. However, the use of this nique is less desirable because the monostearate l-uct being difunctional, it cannot be used to control :cular weight or position fatty chains on the terminal tions of the resin chain and these products have a ter susceptibility to saponification. Such saponificaproducts are morehydrophilic and darker in color l corresponding products of saponified fatty alcohols. able -fatt'y alcohols include octyl alcohol, decyl al- )l, lauryl alcohol, myristyl alcohol, ceryl alcohol, I alcohol, stearyl alcohol, dodecyl alcohol and mixthereof. I arious tricarboxylic acids or anhydrides having a o aromatic nucleus may be used in carrying out this ntion. However, the anhydride form is preferred a less water of reaction is formed. It also offers greater :tivity in the points of reactivity with the polyol olymer. A very suitable tricarboxylic compound for ying out the invention is trimellitic anhydride. Other lble tricarboxylic compounds are trimesic acid and ellitic acid. Further reference to tricarboxylic comsds in the specification, exclusive of the examples, be considered to be denoted when the specific emment trimellitic anhydride is described. he acid number of the invented resins may be furm'odified by substituting aromatic dicarboxylic acids anhydrides for a portion of the tricarboxylic aromaicid. This substitution permits a lower acid number I to be prepared without appreciable change of strucor molecular weight from the parent resin. Addially, the substitution makes possible a second modiion of the resin-a resin with the same number of radicals as the parent resin but having a higher :cular weight. Up to 50 mole percent of the tricar- {lie acid may be substituted but preferably less than nole percent will be substituted. i he use of the term selected dicarboxylic aromatic s and anhydrides as employed herein is to be underd to means (A) terephthalic acid (B) isophthalic (C phthalic acid, (D) Nadic acid, the tradename led to endo-cis-bicyclo(2.2.1)hept--ene-2,3-dicarzoxylic acid, (E) tetrahydrophthalic Acid, (F) hexahydrophthalic acid, and (G) the corresponding anhydride forms of the above listed acids. The use of other dicarboxylic compounds may result in resins that are crosslinked, that are gelled, or lack desirable physical properties such as color and hardness.

Suitable hydroxyls for reacting with the above listed acids and anhydrides to prepare the desired low molecular weight polyol polyester are aliphatic hydroxyls and these may be further characterized as saturated hydroxyls having two to six carbons. Preferably, these glycols have two hydroxy groups and are so located as to be unsymmetrical. Suitable glycols include 1,3-butylene glycol, propylene glycol, ethylene glycol, and mixtures thereof. The polyester generally contains one to five repeating esterified acid hydroxyl units and the hydroxyl group.

It is convenient in discussing the resins of this invention to describe the variousreactants and components in terms of what remains thereof after the reaction has been completed. The term residue has been employed to idenpolyester is terminated by a tify the main portion of the reactant after the characteris'tic radical, such as acid radical or hydroxyl radical has been chemically consumed.

It is to be appreciated that the molecular weight and the regularity of repeating groups in the resins of this invention can be varied over a considerable range. In fact, a completely regular and repeating unit of prepolymerand trimellitic anhydride is not preferred, since the symmetry reduces the solubility of the invented resins.

The molecular weights of these resins will desirably be' relatively low, that is, between about 450 and about 1350 and preferably from about 600 to about 1200. The trimellitic anhydride and polyol polyester are reacted in proportions such that the solid resin product has an acid number (milligrams of KOH per gram of resin) of about to- 250. Solid resins having an acid number from about to about 160 are preferred for the preparation of high quality surface coatings. The desired acid number is achieved by reacting from about slightly over one to two moles of glycol with one mole of selected dicarboxylic aromatic acid or anhydride, to prepare the polyol polyester prepolymer, and then reacting small amounts of I fatty alcohol and about one mole of trimellitic anhydride,

The use of less than one mole of trimellitic anhydride often yields resins which are partially insoluble in ammonia. Likewise, very high mole weights of trimellitic anhydride are undesirable since the resulting resins may form unstable solutions in polish formulations. These resins have a melting point range of between about 65 to about degrees centigrade, with a range between about 80 and about 110 degrees centigrade being pre-- ferred.

Any convenient temperature which will permit the reaction to take place under melt fusion conditions may be employed in preparing the resin of this invention. More desirable is the range between 100 and 250 degrees 'centigrade so that the resin may be readily formed, yet not discolored by oxidation. Thus, this invention provides resinous alkali soluble polymerized partial ester product suitable for preparation of alkaline solutions which comprises (A) a polyol polyester comprised of I saturated aliphatic glycol residues connected by ester linkages to dicarboxylic residues selected from the group consisting of terephthalic acid, isophthalic acid, phthalic l acid, phthalic anhydride, endo-cis-bicyclo-(2.2.1)hept- 5-ene-2,3-dicarboxylic acid, endo-cis-bicyclo-(2.2.1)hept- 5-ene-2,3-dicarb'oxylic anhydride, tetrahydrophthalic aromatic residues a portion of whose carboxyl radicals non-esterified with the said polyol polyester are esterified with a saturated fatty alcohol having 8 to 20 carbon atoms in an amount of from about 0.05 to about 0.50 moles of fatty alcohol for each mole of tricarboxylic compound, and the remainder of the carboxyl radicals on the tricarboxylic compound are in the form selected from the group of free carboxyl and anhydride groups, and is characterized by an acid number of from about 105 to about 250, a molecular weight from about 450' to about 1350, and a mleting point range from about 65 to about 130 degrees centigrade.

A final polish composition of the invention contains in addition to the invented resins, waxy polymers such as polyethylene and polypropylene, hard polymers such as polyvinyl chloride, polyacrylic resin or polystyrene, which are derived from ethylenically unsaturated monomers, leveling agents, materials, to reduce slipperiness, compounds to improve gloss, emulsifiers, alkaline materials and water, as the polish solvent. Generally the total solids content of the polish ranges from about six to about 25 percent by weight of the composition, while the preferred total solids of the polish is from about 9 to about 18 percent. The remainder of the composition is usually water.

The invented resins may constitute from 10 to about 70 percent by weight of the total solids in the polish compositions. Particularly good results are obtained when from about to about 60 percent of the total solid content of the polish are the invented resins. The balance of the total solids is composed of polyethylene and polymers such as polystyrene or polyvinylacrylic which are derived from ethylenically unsaturated monomers, the amount of polystyrene usually being in excess of the amount of polyethylene present.

In order to afford storage stability of the water emulsion polish composition, it is adjusted to a pH of at least seven and more usually to a pH from about 7.5 to about 10.

The final water emulsion polish composition of the invention is normally prepared by making a water solution of the resin portion, a water emulsion of a polyethylene portion, and a water emulsion of the polystyrene portion, separately, and then mixing them together to provide the final composition.

The term soluble as employed in this disclosure is intended to include the concept of dispersible material in the solvent as well as complete dissolving of the material in the solvent.

RESIN SOLUTION A solution of the invented ammonia soluble resin is readily prepared for use in a polish emulsion system. In a typical preparation, 100 parts of an ammonia soluble resin and 500 parts of water are charged to a vessel which will not permit loss of voltatile materials. While agitating the mixture in the vessel, about 25 parts of a 28 percent ammonium hydroxide solution is added to the vessel and agitation is continued until the solution of the resin is complete. Gentle heating may be employed to speed the solubilization. In the preparation of the resin solution, the ammonia may be replaced in whole or in part by other alkaline materials as volatile organic amines. Suitable volatile organic amines include the aliphatic and hydroxy aliphatic amines having boiling points below about 200 centigrade at a pressure of 760 millimeters of mercury, for example, morpholine, ethoxypropylamine, Z-amino- 2- methyl-l-propanol, ethanoilamine, dimethylolamine, ethylene diamine and triethylolamine. The resin solutions generally contain from about 5 to 25 percent solids, preferably about 15 to percent solids.

POLYETHYLE'NE EMULSION A typical polyethylene wax emulsion is prepared as follows. 13.9 parts of AC polyethylene 629, a low molecular weight polyethylene wax melt point about 213-221 tinued until-a uniform blend is produced, which is added to 81.5 parts of water just below 212 degrees Fahrenheit. The emulsion is then quickly cooled to room temperature with agitation.

POLYMER EMULSION The polymer emulsion or latex, as heretofore noted, may contain polystyrene, polyvinyl chloride, or polyacrylir resins. Particularly suited to the polish compositions 01 this invention are those polystyrene resins having a molecular weight of above 5000, preferably those having 2 molecular weight above 100,000. Generally these resin: have a molecular weight below 600,000. These aqueous emulsions are used to provide high gloss, durability anc' toughness.

A typical polymer emulsion is prepared by charging into an enclosed mixing vessel at room temperature 34.5 parts of U-203 Ubatol, a polystyrene manufactured by the UBS Chemical Corporation, Cambridge, Mass, am with moderate agitation 11.5 parts of water are added t( the vessel. Mixing is continued until the mixture is uni form, whereupon a solution of polish plasticizing agent: comprising 1.1 parts of dibutyl phthalate and 08 part 0: trisbutoxyethylphosphate and 51.6 parts of water is adder to the vessel after which agitation is continued for 21 minutes.

The practice of this invention is illustrated but no limited by the examples given below. All parts are by weight and all temperatures are in degrees centigrade unless otherwise stated.

RESIN PREPARATION Example 1 A two liter, 3 necked flask equipped with a stirrer, iner gas feed, recovery trap, vertical steam heated condense and vertical water cooled condenser was charged wit] 190 grams of propylene glycol. The glycol was heated t degrees and 265 grams of isophthalic acid were added The mixture was then rapidly heated to about 195 t4 200 degrees and held there until the charge became clea and the theoretical amount of water had been removed Then, with the temperature at about degrees, th weight of propylene glycol lost earlier was returned it the flask followed by 76 grams of stearyl alcohol and 33 grams of trimellitic anhydride. The mixture was heater to about to 200 degrees and held there until som sublimate was observed forming on the reaction vesse'. At that point, the temperature was raised to 230 degree and held there for one hour. A vacuum treatment wa applied for several minutes to remove the volatile com ponents and the resin was rapidly poured into a shallot tray. The brittle resin had an acid number of 123, meltin point of 80 degrees and a Gardner color number 9. A: ammonia solution of the resulting resin having 16 per cent total solids was prepared; 11 milliliters of 28 percen ammonia was required for 50 grams of resin. The solu tion had a Gardner Holdt viscosity of A;,; Gardner C010 No. 3, pH of 8.75, and a clear appearance.

Example 2 Using the procedure and reactants ofExample' 1, resin was prepared based on 2.5 moles of propylene gly col, 1.25 isophthalic acid, 1.0 moles trimellitic anhydride and 0.25 mole of stearyl alcohol. The reaction tern perature was 200 degrees. The resulting resin had a melt ing point of 82 degrees, acid number of 90, and Gardne Color No. 3. The brittle resin had a clear appearance ammonia solution of this resin (16 percent solids) Example 3 lsing the procedure and reactants of Example 1 the n was prepared-based on 15.0 moles of propylene gly- 7.5 moles ofisophthalic acid, 6.65 moles of trimellitic ydride and 1.5 moles of stearyl alcohol. The resulting u had a melting point of 76 degrees, acid number of Gardner. Color No. -3, and the brittle resin had a LY appearancei An ammonia solution of this resin (16 :ent solids) had the following properties: pH of 8.7, 'dner Holdt viscosity A Gardner Color No. 3 and earance, clear. 5

V Example 4 Ising the procedure and reactants of Example No. 1, sin was prepared based on 2.5 'moles of propylene gly- 1.25 moles of isophthalic'acid, 1.06 moles of trimelanhydride and 0.125 mole of stearyl alcohol. The thing brittle resin had a melting point of 103 degrees, Lcid'number of 136, GardnerColor No. 3, and appeare, clear. An ammonia solution of this resin (16 persolids) have the following properties, pH of 8.4, dner Holdt-viscosity A Gardner Color No. 3, and earance, clear.

Example 5 [sing the procedure and reactants of Example No. 1, :sin was prepared based on 2.5 moles of propylene :01, 1.6 moles of isophthalic acid, 1.2 moles of trilitic anhydride, and 0.28 mole of stearyl alcohol. The llting resin had a melting point of 86 degrees, an acid rber of 144, Gardner Color No. of 3, and a clear aprance.An ammonia solution of this resin (16 percent is) had the following properties, pH of 9.0, Gardner dt viscosity A Gardner Color Number 3, and a clear earance.

Example 6 3,'and a clear appearance. resin similar to the above resin will be obtained It the propylene glycol is replaced with equal molar mm of 1,3-butylene glycol.

Example 7 'sing the procedure of Example 1, except where indid, a resin was prepared based on 2.5 molesof ethylglycol, 1.6 moles of isophthalic acid, 1.2 moles of lellitic anhydride, and 0.27 mole of stearlyl alcohol. resulting resin had a melting point of 81 degrees, an number of 150, Gardner Color No. 4, and a clear :aran'oe'. An ammonia solution of this resin (16 persolids) and a pH of 9.3, a Gardner Holdt viscosity 15; Gardner Color No. 12, and a milky appearance. resin having a lower melting point than the above 1 may be prepared by substituting lauryl alcohol for ke molar amount of stearyl alcohol in the above nulation.

, Example 8 8 sulting resin had a melting point of 71 degrees, an acid number of 169, Gardner Color No. 3, and a clear appearance. An ammonia solution of this resin (16 percent solids) had a pH of 8.7, Gardner Holdt viscosity of A Gardner Color Number of 3, and a clear appearance.

A similar resin is prepared by substitutingan equal molar amount of Nadic anhydride for phthalic anhydride in the above example.

Example 9 Using the reactants of Example 1, a resin was prepared based on 2.5 moles of-propylene glycol, 1.6 moles of isophthalic acid, 0.8 mole of trimelliticanhyride, 0.7

mole of phthalic anhydride, and 0.3 mole of glycerol monostearate, the reaction temperature was 230 degrees. The resulting resin had a melting point of 71 degrees,

an acid number of 123, Gardner Color No. 10, and.

a clear appearance. An ammoniasolution of this resin 16 percent solids) had a following properties: pH of 9.0, Gardner Holdt viscosity A Gardner Color No. 10, and a clear appearance. Q Example 10 Using the procedure of Example 1, a resin was prepared based on 2.5 moles of propylene glycol, 1.6 moles of isophthalic acid, 0.8 mole of trimellitic anhydride, 0.7

cent solids) had a pH of 9.0, Gardner Holdt viscosity of A Gardner Color of 4, and a clear appearance.

Example 11 Using the procedure of Example 1, a resin was prepared based on 20.0 moles of propylene glycol, 12.8 moles of isophthalic acid, 6.4 moles of trimmellitic anhydride, 5.6 moles of phthalic anhydride and 1.12

moles of stearyl alcohol. Reaction temperatuure was 230 degrees. The resulting resin had a melting point of 73 degrees, an acid number of 137, Gardner Color of 11, and a clear appearance. An ammonia solution of this resin (16 percent solids) had a pH of 9.25, Gardner- Holdt viscosity A;,, Gardner Color No. 3, and a clear appearance.

Commercial (Comparative) resin A commercially available polyester resin based on Wood rosin and having an acid number of was compared in this example. An ammonia solution of this resin at 16' percent solids showed the following: Gardner-Holdt viscosity, A Gardner Color No. 10; pH of 8.8, and a clear appearance.

Water emulsion coating compositions were prepared for the coating of linoleum tile. In each case, the coating composition was prepared by stirring together the desired amount of polyethylene emulsion and polystyrene emulsion and thereafter adding the ammonia soluble resin portion. If desired, however, all three components of the coating solution may be blended simultaneously.

The compositions were applied under regular test procedures to the test linoleum tiles and the following observations were made with respect to the coatings as they were being applied and the coatings after they had been dried. The abilities of the coatings to spread out and to avoid patches of different thicknesses, leveling -were.observed as the coatings were put onto the tiles. The glosses of the coatings were determined as dried without buifing. The abilities to resist .water spotting after drying were determined. Additionally, the abilities of second polish coats to blend in with the previous coats were observed.

Storage stabilities were determined in accordance with American Society Testing Materials Procedure D 1791- 60T. Storage at 52 degrees centigrade for two months is considered appropriate to determine equivalent storage stability at 70 degrees Fahrenheit'for one year. Included 9 y in'the rating symbols provided by this test procedure are OK, meaning no visible change, and G, meaning gel.

10 1 p to two-to-two, said residues having been subsequently connected by ester linkages to (B) tricarboxylic monoaro- TABLE I.--P OLISH COMPOSITIONS (i) 6 percentitotalnsolids.

o yviny aery c.- I Commercial resin, see column 8.

stand continuous wear. Coating compositions containing the resins of this invention were noticeably lighter in color than the coatings based on resin polyesters.

Example 19 A two liter, 3 necked flask equipped with a stirrer, inert gas feed, recovery trap, vertical steam heated condenser and vertical water cooled condenser was charged with 190 grams of propylene glycol. The glycol was heated to 120 degrees and 265 grams of isophthalic acid were added. The mixture was then rapidly heated to about 195 to 200 degrees and held there until the charge became clear and the acid value had dropped to 75:15. Then, with the temperature at about 130 degrees, the weight of propylene glycol lost earlier was returned to the flask followed by 76 grams of stearyl alcohol and 330 grams of trimellitic anhydride. The mixture was heated to about 195 to 200 degrees and held there until some sublimate was observed forming on the reaction vessel. At that point, the temperature was raised to 230 degrees and held there for one hour. A vacuum treatment was applied for several minutes to remove the volatile components and the resin was rapidly poured into a shallow tray. The brittle resin had an acid number of 214-219, melting point of 83 degrees centigrade and a solution color of 2. An ammonia solution of the resulting resin having 17 percent total solids was prepared; 21 milliliters of 28 percent ammonia was required for 76 grams of resin. The solution had a Gardner Holdt viscosity of A Gardner Color No. 2, pH of 8.0 and a clear appearance.

The invented resins show storage stability at higher contents of resin in polish formulations than do polyester resins based on wood rosin.

Various changes and modifications may be made in the method and apparatus of this invention and in the mole ratios of the resins of this invention, certain preferred ones of which have been herein described, without departing from the spirit and scope of this invention.

What is claimed is:

1. A resinous alkali soluble polymerized partial ester product which consists essentially of (A) a polyol polyester comprised of saturated aliphatic glycol residues, said glycol having from 2 to 6 carbon atoms and connected by ester linkages to dicarboxylic residues selected from the group consisting of terephthalic acid, isophthalic acid, phthalic acid, phthalic anhydride, endo-cisbicyclo-(2.2.1) hept-5-ene-2,3-dicarboxylic acid, endo-cis-bicyclo-(2.2.1) hept-S-ene-2,3-dicarboxylic anhydride, tetrahydrophthalic acid, tetrahydrophthalic anhydride, hexahydrophthalic acid, hexahydrophthalic anhydride, and mixtures thereof, with the mole ratio of said glycol compound to said dicarboxylic compound being from slightly over one-to-one matic residues selected from the group consisting of trimellitic acid, trimellitic anhydride, trimesic acid, and mixtures thereof a portion of whose carboxyl radicals non-esterified with the said polyol polyester are esterified with a saturated fatty alcohol having 8 to 20 carbon atoms in an amount of from about 0.05 to about 0.50 mole of fatty alcohol for each mole of tricarboxylic compound, and the .remainder of the carboxylic radicals on the tricarboxylic compound are in the form selected from the group of free carboxyl and anhydride groups, and said partial ester product being characterized by an acid number from about to about 250, a molecular weight from about 450 to about 1350 and a melting point range from about 65 to about degrees centigrade.

2. The partial ester product of claim 1 wherein (A) the polyol polyester is the condensation product of propylene glycol and isophthalic acid,,and (B) the tricarboxylic monoaromatic compound is trimellitic anhydride partially esterified with stearyl alcohol.

3. The partial ester product of claim 1 wherein (A) the polyol polyester is the condensation product of propylene glycol and a mixture of isophthalic acid and tetrahydrophthalic anhydride, and (B) the tricarboxylic monoaromatic compound is trimellitic anhydride partially esterified with stearyl alcohol.

4. The partial ester product of claim 1 wherein (A) the polyol polyester is the condensation product of ethylene glycol and isophthalic acid, and (B) .the tricarboxylic monoaromatic compound is trimellitic anhydride partially esterified with stearyl alcohol.

5. The partial ester product of claim 1 wherein (A) the polyol polyester is the condensation product of ethylene glycol and isophthalic acid, and (B) the tricarboxylic monoaromatic compound is trimellitic anhydride partially esterified with lauryl alcohol.

6. The partial ester product of claim 1 wherein (A) the polyol polyester is the condensation product of propylene glycol and a mixture of isophthalic acid and phthalic anhydride, and (B) the tricarboxylic monoaromatic compound is trimellitic anhydride partially esterified with a mixture of ceryl and stearyl alcohol.

7. The partial ester product of claim 1 wherein (A) the polyol polyester is the condensation product of propylene glycol and a mixture of isophthalic acid and endo-cisbicyclo-(2.2.1)hept-5-ene-2,3-dicarboxylic anhydride, and (B) the tricarboxylic monoaromatic compound is trimellitic anhydride and partially esterified with a mixture of ceryl and stearyl alcohol. v

8. The partial ester product of claim 1 wherein (A) the polyol polyester is the condensation product of pro pylene glycol and a mixture of isophthalic acid and phthalic anhydride, and (B) the tricarboxylie monoaromatic compound is trimellitic anhydride partially esterified with glycerol monostearate.

9. In an aqueous emulsion coating composition comprising a waxy polymer, a hard polymer derived from ethylenically unsaturated monomer, a solid resin, emulsifier and water, said resin and mixture of waxy and hard 1 1 1 ymers being present in a weight ratio from about 90 to about 70:30, the improvement wherein said 11 consists essentially of the esterified residues of (A) ow molecular weight polyol polyester obtained by :rifying a dicarboxylic compound selected from the up consisting of terephthalic acid, isophthalic acid, halic acid, phthalic anhydride, endo-cis-bicyclo- 2.1)hept-5-ene-2,3-dicarboxylic acid, endo-cis-bicyclo- 2.1)hept-5-ene-2,3-dicarboxy1ic anhydride, tetrahydrohalic acid, tetrahydrophthalic anhydride, hexahydrohalic acid, hexahydrophthalic anhydride, and mixtures ed with slightly over one to two moles of a'saturated hatic glycol having from 210 6 carbon atoms, foled by reaction with (B) a monoaromatic tricarboxylic ipound selected from the group consisting of iellitic acid, trimellitic anhydride, trimesic acid, and tures thereof with a portion of whose carboxyl radinon-esterified with the said polyol polyester are esterwith (C) a saturated fatty alcohol having 8 to '20 on atoms in an amount of from about 0.05 to about moles of fatty alcohol for each mole of tricarboxylic ipound, andthe remainder of the carboxyl radicals on tricarboxylic compound are in the form selected from group of free carboxyl and anhydrid'e groups and is racterized by an acid number of from about 105 to at 250, a molecular weight from about 450 to about 1350 and a melting 130 degrees centigrade,-"said coating compositionhaving a pH of at least 7.

point range from about 65 to about References Cited UNITED STATES PATENTS Bolton 260-77 OTHER REFERENCES 9 I Boenig, Unsaturated Polyester: Structure and Proper- 20 ties, Elsevier Publishing C0,, New York, 1964, pp. 133

and 135. I ALLAN LIEBERMAN, Primary Examiner 

